Polymers of carboxyamido-and sulfonamido-styrene



Patented Sept. 5, 1950 UNITED STATES PATENT OFFICE POLYMERS OF CARBOXYAMIDO- AND SULFONAMIDO-STYRENE Joseph B. Dickey and Theodore E. Stanin, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 7, 1945, Serial No. 581,568

4 Claims. (Cl. 260-855) 1 2 This invention relates to resins derived from tion procedures such as by light, heat, oxygen, styrenes containing in the styrene molecule on the pressure, organic and inorganic peroxides or some ring one or more sulfonamide or carboxyamide combination of the above. If desired, one of the groups, either polymers or ccpolymers, which commonly known polymerization agents such as resins are particularly useful for the spinning of 5 boron trifiuoride, tin chlorides, or aluminum textile fibers. chlorides may be employed.

It has been previously recognized that styrene The sulfonamide radicle may be introduced into polymerizes to give resins having good strength. the styrene molecule by any method commonly It has also been recognized that when styrene is recognized for this purpose which will not interpolymerized with a small amount of acrylic acid fere with the unsaturated bond. A satisfactory nitrile that the heat stability of the resulting method of preparing compounds of this type is product is slightly higher than that of polymerby starting with ethyl benzene and sulfuryl chloized styrene. Fibers prepared from styrene resins, ride and proceeding through the following series particularly from styrene-acrylic nitrile resins, of reactions, these being reactions the use of give fibers with good strength and stretch, but which is commonly recognizedinorganic chemisthese fibers have been found to be poorly resistant try: s

to elevated temperatures, both in the presence of water and under dry conditions. @0211! solo], @CH-OH;

One object of our invention is to provide poly- 1 803B 80am OHOlOH| also. error-on, +{ggg f cncicn,

sour OHClOHi Nmco. so: cnoiom ordinarily met within polymeric styrene products. Other objects of our invention will appear herein.

We have found that the heat resistance of the polymers and copolymers of styrene can be con- C siderably enhanced by introducing into the sty- Q H01 R :L H CH0! rene molecule one or more sulfonamide or car- 001 O,N R boxyamide groups. In addition, the phenyl radicle of the styrene may contain other substituents such as halogen (F, Cl, Br.), hydroxy, 40

mers f the styrene type in which the heat resist- 30 ance is considerably greater than that which is Q Q oma 0,01

alkyl, alkoxy, phenyl, and the like. The C=C- CHOICE: a base such CECE.

group may be substituted with other groups ,ina pyridine The styrenes having sulfonamide or carboxy- I amide groups thereon may, in accordance with our invention, be either polymerized or they may n be oopolymerized with vinyl compounds using one In the above formulas, R and B. may be sky},

of the various polymerization procedures dearyl, heterocyclic, (tetrahydrofurfuryl) alkylene,

scribed inthe prior art. The polymerization may 7 (methylene, ethylene) hydrogen, hydrazine, be carried out en masse, by abead polymeriza- (phenyl hydrazine) or the like and these groups tion, in the form of a dispersal or solution, under may be either substituted or unsubstituted, the normal pressure conditions or under pressure mm sole criterion being that these substituents do ditions ranging from normal up to ,5000 atmosnot interfere with the course of the reaction.

pheres or more. The polymerization may be ini- This reaction can be generally applied to intiated by one or more of the common polymerizatroduce more than one sulfonamide group, and,

3 if desired, substituted alkyl benzenes such as difluoride, vinylidlne dichloride, vinylidine fluothose represented by the general formula: ride chloride, styrene, vinyl methyl ether, p-cyanovinylmethyl ether, vinyl-,B-cyanoethyl ether, Q nn (2 or more carbon atoms) vinylmethylsulfone and sulfoxlde, methyl acry- 5 late,

a wherein X is selected from carbonl, alkyl, halo- HiNCc1n-o-o-o=0ni gen, acylamides, ketone, sulfone, etc., substituted in either of the ortho, meta, or para position may be employed as the starting material for pre arethylene, tetrafiuoroethylene, methyl iumarate,

mg sulfonamide desired, iumaramide, acrylic acidamides, acrylonitrile, For the preparation of the carboxyamide, ethyl crotononltrile, vinyl urethane, fumaronitrile,

benzene or a. substituted ethyl benzene may be yanoa ry d m d s. B- ya yl ryused as the starting material and the following lates and the 1316- the Preparation 01 fibrous set of equations may be employed to obtain the materials acrylonitrile has been found to be or desired compound: value, and, therefore. this material is employed :L o,m+ $0,013 onololn CHClCHz-i-SOOh N)16 N)l5 00191-5 Qcnolom g -mr QOHOICH; tort. mums on=om O01)16 0N-R oN-R In the above formulas, R and R. may be any for copolymerization with the sulfamido and of the groups designated by these characters in carboxyamido styrenes for the making of fabthe explanation of the reactions for preparing rics. In preparing the polymers one or more or the sulfonamides. Each of the steps designated I the above monomers may be copolymerized with above are well known organic reactions and are one or more of the sulfonamido, styrenes, or the carried out in accordance with the methods orcarboxyamido styrenes in any desired amount. dinarily employed in organic chemistry. In the For instance, in some cases equal parts of the above preparation of carboxyamides a substivinyl monomerandthe sulfonamide styrene prove tuted alkyl benzene might be employed as the to be satisfactory. This also holds true in the starting material, as was explained with reference case of carboxy styrenes. In other cases but a to the starting material of the sulfonamide. small pr p Such 10-30% of the sulfon- The placing of sulfonamido groups on alkyl amido styrene 0 boxyamido Styrene is sumbenzenes is known in the art as shown in Beilcicnt to give the desired results. The follow n stein, vol. 11, pages 119 and 120, wherein an arx mpl s illustrate the preparation of resins in ticle by Sempotowski, Berichte, vol. 22, p e 2672 ac or n with our invention.

is referred to. The conversion of the ethyl group Example 1.-Eighteen parts of p-sulfamido of ethyl benzene to an unsaturated radicle is styrene were mixed with 6 parts of acrylonitrile shown in Ellis The Chemistry of Synthetic and 0.02 part of benzoyl peroxide. The mass was Resins," vol. 1, pages 252 and 253. On page 252, heated in a sealed tube at C. for two days. line 27, this text points out that chlorethyl ben- When cooled, the tube was opened and the tough zene forms when ethyl benzene is chlorinated be- 50 S lid pro Was Purified y dissolving in pyrilow 30 C. Further on, this text points out that dine and poured into water. Instead of pyridine treatment with pyridine will cause the formasome other suitable solvent might be employed as tion of the unsaturated suhstituent. Also on a substitute therefor in the process. If desired, page 253, lines 12 to 14, this text shows that this during the polymerization the tube may be exprocedure is useful for analogues of styrene. posed to ultraviolet light to facilitate the poly- Berichte 29, 2535, in an article by Gube, shows merization operation. To obtain fibers from this ethyl benzene containing carboxyamide groups Polymer it is dissolved in acetone and the fibers was known in 1896. This, coupled with the disare spun from that solution.

closure in Ellis given above, constitutes a teach- Example 2.-Twenty-one parts of a mixture of ing to anyone skilled in the art 01 the prepara- 0-, m-, and p-ethylsulfamido styrenes were mixed tion or the carboxyamido compounds used as the with 18 parts of acrylonitrile, and 0.03 parts of starting material in the preparation of polymers benzoyl peroxide. The mass was polymerized by as described herein. the procedure employed in the preceding exam- If it is desired to prepare the copolymer, the 9 The P lymerization was stopped when a sulfamido or carboxyamido styrenes may be sample shows that the polymerization is about polymerized with vinyl monomers, the latter 60% co p The P y s covered from preferably in small proportions such as up to the mass by the method employed in the preced- 20% of the total mixture. The styrene carboxy ing example. I! desired, in a polymerization of and sulfonamide compounds may be present in this type, some other material such as phenylany desired amount. Some of the polymerizable a-naphthylamine or hydroquinone might be addm'onomers, both vinyl and non-vinyl which may ed at the desired moment to destroy the catalyst be employed for copolymerizing with the carboxyand stop the polymerization. amido and sulfonamide styrenes are the follow- Example 3.-FiIteen parts or p-carboxyamido ing: lso-butylene, vinyl acetate, vinyl methyl styrene were mixed with 10 parts of methyl acryketone, vinyl chloride, vinyl fluoride, vinylidine late and 5 parts of N-propylacrylamide, 0.03 part of a mixture of benzoyl peroxide and acetyl peroxide were added and polymerization was started by raising the temperature to 40 C. and continuing to increase the temperature to 75 C. over a period of several days. The product was worked up as described in the preceding examples.

Example 4.--A mixture of 21 parts of p-di-N- methylsuliamido styrene, 20 parts of methyl isopropenyl ketone and 0.03 part of benzoyl peroxide were heated at 50 C. for several days in a sealed tube and then slightly raised to 75 C. A hardtough product was obtained suitable for the preparation of films, fibers, or molded products. The resin is recovered from the polymeric mass in the same manner as described in the preceding examples.

Example 5.A mixture of 5 parts of N-CHr-C ONE:

6 parts of vinyl chloride, and 8 parts of vinyl acetate were polymerized in the presence of 0.05 part of benzoyl peroxide in a closed vessel beginning at 30 C. The temperature was slightly raised to 80 C. A slightly yellow tough solid resulted which was purified by the procedure specified in Example 1. This solid was suitable for use in preparing fibers, films, molded products or the like.

Example 7.A mixture of 5 parts of toN 50 parts of vinylidine dichloride, 1 part of acrylonitrile, 0.1 part of benzoyl peroxide, 200 parts of water and 0.4 part of gum arabic were placed in a container with about 10% free space and tumbled at 50 R. P. M. at a temperature of approximately 50 C. Polymerization is continued until complete and the product is removed in the form of beads. It is advantageous to carry out iii a polymerization of this type at an elevated pressure such as 1000 atmospheres or more using an autoclave, imparting pressure by pumping in inert gas such as nitrogen. methane, or the like.

6 Example 8.-'-Three parts of CH: 2 parts of 31 parts of styrene, 0.5 part of urea. peroxide,

parts of water, 0.9 part of gelatin, 0.05 part of- 2-ethylhexanol, 0.189 part of sodium ethyl naphthalene sulfonate, and 0.067 part of carbon tetrachloride were mixed together so as to form an emulsion, and this mixture was shaken for $4 days at 50-60 C. The resulting polymer was precipitated by adding dilute mineral acid there to to break the emulsion. The precipitated product was then filtered. washed, and dried.

Example 9.A'n emulsion was formed consisting of 6 parts of 16.2 parts of butadiene, 2 parts of fumaronitrile, 0.5 part of urea peroxide, 0.9 part of gelatin, 0.05 part of ethyl hexanol, 0.07 part of carbon tetrachloride, and 0.2 part of sodium ethyl naphthalene sulionate, and the emulsion was shaken for 3-5 days at a temperature of 50-60 C. The polymer formed was precipitated by adding dilute hydrochloric acid to the mass to break the emulsion. Hydroquinone was added to destroy the catalyst. The resulting yellowish polymer was filtered oil, washed, and dried. The tough solid thus obtained was suitable for preparing fibers, films, or the like and also was susceptible to vulcanization. Instead of butadiene, butadiene derivatives may be employed to prepare polymers as outlined in this example. Some of the butadienes which might be employed are 2-chlorobutadiene, 2-chloro-3-fiuorobutadiene, 1 and 2- acetoxybutadiene, 2 or ,3-chloro-4-acetoxybutadiene, '2-methyl-3-chlorobutadiene, and2-cyanobutadiene. j

Example 10.Five parts of were placed in a shaking autoclave and ethylene was pumped in until a pressure of 1500 atmospheres was reached. The reaction mixture was heated at C. for approximately 23 hours, cooled, and the reaction product was removed. The resulting material was a hard,iough solid capable of being spun into fibers from solution. This reaction was repeated except that in one case propylene was employed, another of ethylene and in the other case iso-butylene was used in this manner. In each case a product similar to that obtained in Example 10 was obtained.

Example 11 .-Ten parts of JBONH:

20 parts of vinyl acetate, and 20 parts of vinyiidine dichloride were mixed together and heated in a sealed tube with 0.05 part of benzoyl peroxide at 50 C. for several days. The resultinl polymer is a tough solid suitable for preparing filaments.

Example 12.--Five parts of were mixed with parts of .methylacrylate, 5 parts of methyl fumarate, and 5 parts of methyl vinyl sulfone, and the mixture was polymerized together in the manner described in the preceding example. The product was a slightly yellow tough solid capable of being molded.

Example 13.Ten parts of ONE:

were mixed with 20 parts of vinyl methyl ether and 50 parts of styrene, and the mixture was polymerized in the presence of 0.04 part of henzoyl peroxide in the same manner as the polymerization was carried out in Example 1.

Example 14.Ten parts of parts of p-(N-p-tolylsulfonamido) styrene, and 0.01 part of benzoyl peroxide were all mixed together by dissolving in acetic acid. The solution was slowly heated up to 150 C. over a period of several days. The mixture was cooled and purified as described in the preceding examples.

A yellowish high-melting solid was obtained.

We claim: 1 l. A polymer suitable for the spinning of tex tile fibers therefrom resulting from the polymerization of a mixture of approximately 945%,

based on the total polymerization material there- 8 in, of styrene containing on the ring thereof 1-2 groups selected from the group consisting of sulfonamide and carboxyamidc, when 2, the groups being one of each, and a compound containing a polymerizable group represented by the formula:

2. A polymer suitable for the spinning of teltile fibers therefrom resulting from the polymerization of a mixture of approximately 945%, based on the total polymerization material therein, of styrene containing on the ring a sulfonamide group and a compound containing a polymerizable group represented by the formula:

3. A polymer suitable for the spinning of textile fibers therefrom resulting from the polymerization of a mixture of approximately 845%, based on the total polymerization material therein, of styrene containing on the ring a. carbonyamide group and a compound containing a polymerizable group represented by the formula:

JOSEPH B. DICKEY. THEODORE E. STANIN.

No references cited. 

1. A POLYMER SUITABLE FOR THE SPINNING OF TEXTILE FIBERS THEREFROM RESULTING FROM THE POLYMERIZATION OF A MIXTURE OF APPROXIMATELY 9-75%, BASED ON THE TOTAL POLYMERIZATION MATERIAL THEREIN, OF STYRENE CONTAINING ON THE RING THEREOF 1-2 GROUPS SELECTED FROM THE GROUP CONSISTING OF SULFONAMIDE AND CARBOXYAMIDE, WHEN 2, THE GROUPS BEING ONE OF EACH, AND A COMPOUND CONTAINING A POLYMERIZABLE GROUP REPRESENTED BY THE FORMULA: 